Process for the production of secondary and tertiary alkyl monochlorides



. PatentedDec. 2s, 1.937 1 1 6 H w 2,103,692 I PROCESS FOR THE raonuo'rlonbr sno- ONDARY AND TERTIARY CHLORIDES ALKYL MONO- :rinjjm. 56.0,5Zil lh Germany October 15,

11 Claims. (01.260-166) The development of the cracking processes'has resulted in the factthat. large quantities ofjg'ase ous and liquid olefines are available for the 'industry. V .Owingto their reactive capabilities these 6 ol efinesiform an admirable starting material for chemical synthesis. ,Alkyl chlorides, which can be" obtained by adding-hydrogen halides to the olefine double bond, form thefstartingv point of very-many-syntheses inorganic chemistry. It is 1 known that, of the. hydrogenhalides, hydrogen iodidelis the most easily added. ,7 The addition of hydrogen bromide takes place less readily and hydrogen chloridecan only be added with great difllcult'y. Thisiactis confirmed inthe experiments' carried out by Erlenmeyer, An'nalen 139,

page 228 (1846) Butlerow,.Annalen 145,.page 274 (1868), Markownikow, v Annalen,153, page 256 (1869), BerL'Ber. II, page 660 (1869) and .Saitzefi,

"Annalen 179, page 296 (1875)., Theq'above in- ,vestigatorscarried"outtheir operations: by causing the volefines l to react with aqueous" concentrated hydrochloride acid; In the; later workcarried out in connecti" n with the addition ofhyd'rogen chloride to olefines' the latterwere treated withconcentrated hydrochloric acid, zinc chloride being added totl' e hydrochloric acid by some investigators.

179, page 321, 1875, Kondakoff, Annalen 25, page The German Patent No. 219,955 or the Bad.

:Anilin und Sodaiabrik, according to which the 1 during the reaction, are converted in the presence fraction of cracked benzines, boiling up to 45 0.,

is treated with concentrated HCl, whereby tertiary amyl ehloride'is said to be formed, is based on these experiments.

The'oleflnes themselves, according to all the hitherto known publications, were caused to rerhact with HCl in that state .oi'aggregation, in which they exist under normal, conditions of pres 4 sure. and temperature, 1. methylene and propylene in the gaseous state (nothing has hitherto been publishedconcerning the addition of HCl to butylene) and amylenes and higher homologues in the liquid state. According to the deso small that their use in industry could not ethylene andpropylene by similar methods into chloride and propyl chloride respectively. a

ithfioifetical yieldbf alkyic ilorides. ofithediand polyvalent metals, such'as ZnClz, CdCl-z, B1013, sncu, T1014, UCl4,WCl4, vcu. M0015, (Wagner and Saitzeff, .Annalen scribed processes theyield of alkyl chlorides was contemplated. Within recent years attempts have been made by Berl'and Ritter. '(Berl, Ber.

'In this my employing pureolefines, they SllC-e ceeded in obtaining yields up to 35% of theory, As carriers for the catalysts inert materials, such as glass and. asbestos, were employed. i The work done in this'fleld hitherto thus .did

not result in such yields 'oialkyl'chlorides as would justify contemplating their application in industry. The comparatively {low yields were; probably due to the fact that the catalysts and catalyst carriers were, not sufiiciently active and also that the amylene's andhigher .homologues in the liquid phase reactvery sluggishly with HCl. Experiments were therefore, carriedout-inihis direction and resulted in the present invention.

It has been found to be advantageous to cause also those olefines which are liquid at ordinary temperatures, to react in the vapor phase with HCL Highly porous "substances, such as active 7 carbon, silica gel,- etc., were found to be particularly suitable as "carriers; These substances al ready possess in themselves a strong catalytic action and give rise in one operation. even without furtheradditions, to more than of the If chlorides SbCls etc. are deposited in a finely divided condition on the above highly activecarriers, theoretical yields are obtained. In place of the chlorides, use maybe made of any other salts of these metals, for example nitrates or sulphates, which,

of HCl into the active chlorides. The high activity of the catalysts employed also enables ole-' fines --to be treated in a diluted conditiongi. e. admixed with non-olefinic compounds, for example with aliphatic, aromatic, naphthenic and Examples 1.--l00 cubic metres of waste gas from a cracking distillation process containing 12% by volume of unsaturated hydrocarbons, of which 2% are ethylene, 8% propylene and 2% butylene, are passed together with the theoretical quantity of thoroughly dried gaseous hydrogen chloride over active carbon, which has been impregnated with 20% anhydrous such. This catalyst is disposed in an earthenware tube heated to about 150 C. The gaseous reaction mixture is washed with water and soda. solution and the resulting chlorides are separated by condensation or absorption by active carbon.

The total yield of chlorides amounts to 38.5 kgms, from which there are obtained by suitable fractionating: 5 kgms. of CzHsCl, 26.2 kgms. of CaHrCl and 7.3 kgms. of C4HBC1 corresponding to a 91% yield of chlorides.

2.-100 kgms. of a fraction of a cracked benzine, boiling between 20 and C. (containing 01' pentanes and 35% of amylenes) are passed in vapor form, mixed with the calculated quantity of H01 gas, over silica gel, which has been previ- 1 ously saturated with 10% of a mixture otanhydrous ZnCl: and Tick. The catalyst is disposed in two copper tubes silvered inside, the first of which is maintained at about 150 C. and the second at about C. The former temperature- I ems distillation oi brown coal, boiling between 40 and 80 C. and containing 70% of hexanes and 30% and tertiary alkyl monochlorides from normally liquid oleflnes which comprises vaporizing said oleilnes and passing the vapor mixture with hydrogen chloride over a polyvalent metalhalide catalyst deposited upon substances of high surface activity selected from the group consisting of silica gel and active carbon.

aid of H01.

3. kgms. of a traction of benzine from the 2. A process for the production of secondary and tertiary alkyl monochlorides from normally liquid oleflnes in admixture with other hydrocarbons which comprises vaporizing said oleflnes and passing the vapor mixture with hydrogen chloride over a polyvalent metal halide catalyst deposited uponsubstances of high surface activity selected from the group consisting of silica gel and active carbon.

3. A process as claimed in claim 1, in which the metal halide catalyst consists of zinc chloride.

4. A process as claimed in claim 1, in which the metal halide catalyst consists of titanium chloride.

5. A process as claimed in claim 1, in which the metal halide catalyst consists of tin chloride.

6. A process as claimed in claim 1, in which the chlorides are produced during the reaction by converting other metal salts into chlorides by the aid of HCl.

7. A process as claimed in claim 2, in which the chlorides are produced during the reaction by converting other metal salts into chlorides by the 8. A process as claimed in claim Lwherein dry, gaseoushydrogen chloride is employed.

' 9. A process as claimed in claim 2, wherein dry, gaseous hydrogen chloride is employed.

v 10. A process as claimed in claim 1, wherein oleilne mixtures, from which secondary and tertiary chlorides can be formed, are conveyed at at least two temperatures diflering from each other by at least 40 degrees centigrade over the catalysts, the oleilne vapors first passing over the catalyst which is heated to the higher tempera- I 11. A process as claimed in claim 2, wherein oleflne mixtures, from which secondary and tertiary chlorides can be formed. are conveyed at at least two temperatures diflering from each vother for at least two temperatures diflerlng from each other for. at least 40 degrees centigrade over the catalysts, the oleflne vapors first passing over the gatalyst which is heated to the higher tempera- WACLAW JUNOSZA PIOTROWSKI. JOZEF WINKIER. 

